Nitrohydroxyethers



. methyl-l-propanol, .dnoxymethyDnitromethane, 2 nitro 2 propyl 1 pro- Patented Jan. 3, 1967 3,296,313 NITROHYDROXYETHERS John1A. Frump,,,Terre Haute, Ind., assignor to Commercial Solvents Corporation, a corporation of Maryland No Drawing. Filed Aug. 15, 1963, Ser. No. 302,470 2 Claims. (Cl. 260-615) This application is a continuation-in-part of copending application SerialNo. 8,234, filed February 12, 1960, now

abandoned.

My invention relates to a new group of nitrogen compounds. and a process for their preparation. More particularly, it relates to a catalytic process for oxyalkylating nitroalcohols and nitropolyols with epoxides and the novel nitro and amino hydroxyethers obtained thereby.

The :novel nitrohydroxyethers, compounds A, of the invent-ion are those having the following general formula:

wherein R .is a member selected from the group consisting of .methyl and hydrogen; wherein R is a member selected from the group consisting of alkyl radicals, for instance. of, about 1 to 10 or 20 carbon atoms including lower alkyl radicals; lowerhydroxyalkyl radicals, for instanceof up to 5 carbon atoms; and a radical having the general formula:

wherein Rg in the above formula and radical is a member selected from the group consisting of the radicals wherein R is a member selected from the group consisting of hydrogen, phenyl, nitro-substituted phenyl, halosubstit utedphenyl; alkyl, hydroxyl-substituted alkyl, halosubstituted alkyl, alkene, and phenyl-substituted alkyl radicalsyy is an integer ranging from about 1 to or 20, and x in the above formula and radical is an integer ranging from about 1 to 20.

wherein R, has the above meaning and wherein R is a member selected from the group consisting of alkyl radicals of 1 to 20 carbon atoms, for instance including lower alkyl radicals; and lower hydroxy alkyl radicals, for instance having from about 1 to 5 carbon atoms; and x is aninteger ranging from about 1 to 20, in the presence of catalytic amounts of boron trifluoride or p-xylenesulfonic acid. Examples of suitable nitroalcohols are 2-nitro-2- 3-nitro-3-metbyl-2 butanol, tris(hypanol, 2-1nitr o-2 methyl-l-octanol, 2-nitr-o-2-propyl-1-tridecanol, I2 nitro 2 ethyl 1 nonadecanol, 12 nitro- 1-2 1 methyl 1 tridecanol, 18 nitno 18 methyl 1 nonadecan-ol, 6 nitro 6 ethyl 1 heptanol, tris(hy- United States Patent Office droxyethyl)nitromethane, tris (hydroxybutyDnitromethane, and the like.

In the process for producing my new nitro compounds, I generally employ temperatures ranging from about 0 C. to about 150 C. At temperatures above 150 C. decomposition of the new compounds may occur. Temperatures below 0 C., even though allowing formation of my new compounds, would not be economically practical due to the requirement for expensive cooling equipment. While a broad temperature range of from about 25 C. to about 150 C., for instance, is suitable for my process, I prefer to use temperatures ranging from about 50 C. or C. to about C. When temperatures below the melting points of the nitroalcohols used in my invention are utilized, I prefer to use a solvent for the nitroalcohol which solvent is inert to the reactants and the reaction product. Examples of solvents which are useful include isopropyl ether, chloroform, dioxane, and the like.

Satisfactory results can be obtained in my process for producing the novel compounds of my invention by using small or catalytic amounts of boron trifluoride or p-xylenesulfonic acid catalyst in the reaction mixture. It was surprising to discover these catalysts since other acidic catalysts were found to be unsatisfactory. Catalytic amounts of boron trifluoride or p-xylenesulfonic acid ranging from about 0.05 to about 0.5% or 5% based on the weight of the nitro alcohol can generally be utilized but boron trifluoride is preferred. However, if desired, more or less than this amount can be used. In utilizing the boron trifluoride catalyst in my process, I prefer to form a complex with a compound inert to the reactants and the reaction products, for example, an ether. Representative ethers which I have found to be useful in forming complexes with boron trifluoride include isoprop-yl ether, dirnethyl ether, diethyl ether, dibutyl ether and the like. I prefer a complex of boron trifluoride-diethyl ether containing about 45 to about 50% by weight of boron trifluoride based on the weight of the complex. Although free boron trifluoride is a suitable catalyst in my process, its complexes with the ethers aforenamed are much easier to handle, use and store under ordinary industrial conditions, thus making them preferable to free boron trifiuoride.

The molecular proportions used in producing the new compounds of my invention can vary considerably depending on the nitroalcohol and epoxide used and/or on the final product desired. Ordinarily, mole ratios of nitroalcohol to epoxide of not less than 1:1 and not more than about 1:10 or 1:20 are useful in my process.

The epoxides from which I prepare my compounds must contain at least one grouping. Representative epoxides include alkylene oxides such as ethylene oxide, butene-l-oxide, isobutylene oxide, butadiene monoxide, 1,2-epoxyoctane, 1,2- epoxytetradecane, 3 ,4-epoxyl-butanol, 1,2-epoxynonadecane, etc.; alkylene dioxides such as butadiene dioxide, etc.; halo-substituted alkylene oxides such as chloropropylene oxide, bromo propylene oxide, etc.; phenyl-substituted alkylene oxides such as 1,2-epoxyethylbenzene, 1,2-epoxyoctylbenzene, 1,2-epoxyheptadecylbenzene, etc.; nitrosubstituted phenyl-substituted alkylene oxides such as 1, 2-epoxyethylnitr0benzene, etc.; halo-substituted phenylsubstituted alkylene oxides such as 1,2-epoxy chlorobenzene, styrene oxide, and the like.

The novel nitro compounds of my invention can be reduced by any suitable reducing procedure to the corresponding amines. Thus, the method of the invention provides a novel and efficient means for obtaining novel amino hydroxyethers, compounds B, having the general formula:

wherein R R x and R have the values assigned to them above. It should be noted that my attempts to obtain these amino hydroxyethers by oxyalkylation of the corresponding amino-alcohols proved unsuccessful since the oxylating agents were found to preferentially add onto the amino group rather than the hydroxyl group. This preferential addition is expected since the amino group is more reactive than the hydroxyl group and it was thus surprising to find that the novel amine compounds of the present invention could be produced by oxyalkylating the novel nitro compounds to the corresponding novel amine compounds of the present invention.

wherein R in each case in an alkyl group of up to 20 carbon atoms and R R and x have the values assigned above; (II) the same formula wherein only one of the R is an alkyl group and the other is lower hydroxyalkyl,

wherein R has the value assigned above; and (III) the same formula as above wherein one R is alkyl, the other is hydroxyalkyl and R is the radical to-om-orr-pon where R and y have the same values assigned above.

The preparation of the aminohydroxy ethers of (I) is effected by oxyalkylating the corresponding dialkyl nitro alcohols with any of the oxyalkylating agents described above in molar ratios also described above, followed by reduction of the nitro group of the resulting nitro hydroxy ether to the amino group. The amino hydroxyethers of (II) on the other hand can be prepared by oxyalkylating the monoalkyl amino-alcohols with butadiene dioxide in a mole ratio of alcohol to butadiene dioxide of 2:1 and reducing the two nitro groups of the resulting nitro compound to amine groups. The amino hydroxy ethers of (III) can be similarly prepared using an hydroxyalkyl, alkyl, nitroalkanol.

In carrying out the reduction step, I prefer to first neutralize any remaining catalyst with a base, such as calcium hydroxide, and then dissolve the nitro compound in methanol and hydrogenate it under hydrogenation conditions, for instance at temperatures ranging from about 25 C. to 100 C. and at a pressure of from about 400 to 500 psi. in the presence of catalytic amounts of a nitro to amine reducing agent, e.g. a nickel catalyst such as Raney nickel catalyst. After the reduction has taken place, the amine can then be purified by any suitable means, such as distillation.

The new nitrogen, i.e. nitro and amino, hydroxyether compounds of the invention are useful as corrosion inhibitors, bactericides, pigment wetting and dispersing agents, emulsifiers and as intermediates in the preparation of nonionic surface active agents. For example, in utilizing either the nitro or amino hydroxyethers as pigment wetting agents in a pigment system, I can add from about 2% to 8% by weight based on the weight of the pigment system of the compounds to a pigment system containing a pigment, such as titanium dioxide and water. The compounds thus act as wetting and dispersing agents for the pigment.

The following examples are offered to illustrate my invention; however, I do not intend to be limited to the specific materials, preparations and procedures shown. Rather, I intend for all equivalents obvious to those skilled in the art to be included within the scope of my invention.

Example I To a closed reactor equipped with an agitator containing 1071 grams of 2-nitro-2-methyl-1-propanol, having a temperature of C., were added 10 milliliters of boron trifiuoride-diethyl ether. Ethylene oxide was then added from a cylinder into the reactor at a pressure between 1 and 5 psi. over a period of approximately 7 hours during which time the temperature of the reaction never exceeded 130 C. An oxyalkylated product containing 2-methyl-2-nitro-4-oxa-6-hydroxy hexane was thereby produced.

15 grams of calcium hydroxide were then added to the reaction mixture and the mixture was thoroughly agitated. Three liters of methanol were then added to the mixture to form a slurry and the slurry was filtered. To the filtrate were then added grams of Raney nickel and the thus-treated filtrate was hydrogenated at a pressure of approximately 400 to 500 p.s.i. at an initial temperature of 25 C. As the reduction proceeded, the temperature was gradually increased to approximately 50 C. The hydrogenation required a period of about 2 hours, during which time the reaction mixture was constantly agitated. After absorption of hydrogen had ceased, the reaction mixture was withdrawn from the container, the catalyst removed from the solution by filtration and the methanol separated from the reaction mixture by means of fractional distillation. The residue thus obtained was subjected to fractional distillation under vacuum. 2-methyl-6-hydroxy-4-oxa-Z-hexylamine in the amount of 100 grams was collected.

The following data was determined for the compounds:

Found: N, 10.51%; H, 11.18%; C, 53.45%. Calculated: N,10.5%; H, 11.3%; C, 54.1%.

Example 11 One mole of 2-nitro-2-methyl-l-propanol is reacted with two moles of 1,2-epoxyethylbenzene in accordance with the general procedure of Example I to produce 2- methyl-Z-nitro-4,7-dioxa-6,9-diphenyl-9-hydroxy nonane. This nitro compound is reduced as in Example I to obtain 2-methy1-9hydroxy-4,7-dioXa-6,9-diphenyl-2-nonylamine.

Example 111 One mole of 2-nitro-2-methyl-l-propanol is reacted with one mole of 1,2-epoxyoctylbenzene in accordance with the general procedure of Example I to produce 2- methyl-2-nitro-4-oxa-6-hexylphenyl 6 hydroxy hexane. This nitro compound is reduced as in Example I to obtain 2-methyl-6-hydroxy-4-oxa-6-hexylphenyl 2 hexylamine.

Example IV One mole of 2-nitro-2-methyl-l-propanol is reacted with two moles of 1,2-epoxyheptadecane in accordance with the general procedure of Example I to produce 2- methyl-2-nitro-4,7-dioxa 6,9 dipentadecyl 9 hydroxy nonaneu This nitro compound is reduced as in Example I to. obtain 2methyl-9-hydroxy-4,7-dioxa-6,9diphentadecyl-Z-nonylamine.

Example V One mole. of 2-nitro-2-rnethyl-l-propanol is reacted withwoneumole of chloropropylene oxide in accordance vvitl lithe general procedure of Example I to produce 2- inethyl 2 nitro 6 hydroxy 4 oxa 6 chlrornethyl- 6-hexyl alcohol. This nitro compound is reduced as in Example I to obtain 2-methyl-6-hydroxy-4-oxa-6-chloromethyl-Z-hexylarnine.

Example VI One. mole of 2-i1itro-2-methyl-l-propanol is reacted with two moles of 1,2-epoxyheptadecylbenxene in accordance with the general procedure of Example l to produce 2 methyl 2 nitro 4,7 dioxa 6,9 di(phenyl pentadecyll-Q-hydroxy nonane. This nitro compound is reduced asin Example I to obtain 2-methyl-9-hydroxy-4,7- dioxa-6,9-di(phenyl pentadecyl)-2-nonylamine.

Example VII Two moles of 2-nitro-2-methyl-l-propanol is reacted with ;one.mole of butadiene" dioxide in accordance with the general procedure of Example I to produce 2,11- dimethyl-2,1 1 dinitro-4,9-dioxa-6,7 dihydroxy dodecane. This nitro compound is reduced as in Example I to obtain 2,1l-dimethyl-6,7-dihydroxy-4,9-dioxa-2,1 l-dodecanediamine.

Example VIII One mole of 2-nitro-2-methyl-l-propanol is reacted with lone mole of 1,2-epoxyethyl nitrobenzene in accord- Example X One mole of 3-methyl-3-nitro-2-butan-ol is reacted with one mole of ethylene oxide in accordance with the general. procedure of Example I to produce 2,3-dimethyl-2- nitro-4-oxa-6-hydroxyhexane. This nitro compound is reduced as in Example I to obtain 2,3-dimethyl-6-hydroxy- 4-oxa-2-hexylamine.

Example XI One mole of 2-nitro-2-methyl-l-hexanol is reacted with onemole of ethylene oxide in accordance with the general procedure of Example I to produce S-methyl-S-nitro- 3- oxa-1-nonyl. alcohol. This nitro compound is reduced as in Example I to obtain -amino-5-rnethyl-3aoxa-l-nonyl alcohol.

Example XII One mole of 2-nitro-2-methyl-l-nonadecanol is reacted with one mole of ethylene oxide in accordance with the general .procedure of Example I to produce l8-methyl- 18-nitro-20+oxa-22-hydroxy docosane. This nitro compound is reduced as in Example I to obtain l8-rnethyl- 22-hydroxy-20-oxa-18-docosylamine.

Example XIII One-mole of 12-nitro-lZ-methyl-l-tridecanol is reacted with one mole ofethylene oxide in accordance with the general. procedure of Example I to produce Z-methyl-Z- nitro-14roxa-16-hydroxy hexadecane. The nitro com- 6 pound is then reduced as in Example I to obtain Z-methyl- 14-oxa-16-hydroxy-Z-hexadecylamine.

Example XIV One mole of 6-nitro-6-ethyl-l-heptanol is reacted with one mole of ethylene oxide as in Example I to produce 2ethyl-2-nitro-8-oxa-lO-hydroxy decane. This nitro compound is reduced as in Example I to obtain 2-ethyl-l0- hydroxy-8-oxa-2-decylamine.

Example XV One mole of 2-nitro-2-methyl-l-propanol is reacted with 16 moles of ethylene oxide to produce 2-methyl-2- nitro-4,7,10,13,16,19,22,25,28,31,34,37,40,43,46,49 hexadeca-oxa-Sl-hydroxy-dopentacontane. This compound is reduced as in Example Ito obtain Z-methyl-Sl-hydroxy- 4,7,10,13,16,19,22,25,28,31,34,37,40;43,46,49 hexadecaoxa-2-dopentacontanylamine.

Example XVI One mole of tris(hydroxymethyl)nitromethane is reacted with three moles of ethylene oxide in accordance with the general procedure of Example I to produce tris(2- hydroxyethoxy-methyl)nitromethane. The compound is reduced as in Example I to obtain tris(2-hydroxyethoxymethyl)methylamine.

Example XVII One mole of tris (hydroxyethyl)nitro methane and three moles of ethylene oxide are reacted following the procedure of Example I to give tris(Z-hydroxyethoxy-ethyl) nitromethane. The compound is reduced as in Example I to obtain tris(Z-hydroxyethoxy-ethyl)methylamine.

Example XVIII Reaction of one mole of tris hydroxyethyDnitromethane with 2 moles of ethylene oxide following the procedure of Example I provides di(2-hydroxyethoxy ethyl) hydroxyethyl nitnomethane. Reduction of this compound as in Example I provides the corresponding amine.

Example XIX One mole of 2-nitro-2-methyl-l-propanol is reacted with one mole of 1,Z-epoxyethyl-p-chlorobenzene in accord ance with the procedure of Example I to produce 2- methyl-2-nitro-4-oxa-6-p-chlorophenyl-6-hydroxy hexane. This nitro compound is reduced as in Example I to obtain 2-methyl-6-hydroxy-4-oxa-6-p-chlorophenyl-Z-hexylamine.

Example XX One mole of 2-nitro-2-methyl-l-propanol is reacted with one mole of butadiene monoxide in accordance with the procedure set forth in Example I to produce 2-nitro-2- methyl-4-oxa-6-hydroxy-6-vinyl hexane. This nitro compound is reduced as in Example I to provide 2-methyl-4- oxa-6-hydroxy-6-vinyl-2-hexylamine.

Example XXI One mole of 2-nitro-2-methyl-1-propanol is reacted with one mole of styrene oxide using 1.2 percent of p-Xylenesulfonic acid as catalyst instead of the boron trifiuoride to produce 2-nitro-2methyl-4-oxa 6-phenyl-6-hydroxy hexane which is reduced as in Example I to provide 2- methyl-4-oXa-6-phenyl-6 hydroxy hexylamine.

Example XXII One mole of 2-nitro-2-methyl-l-propanol is reacted with one mole of 3,4-epoxy-l-butanol in accordance with the procedure of Example I to produce 2-nitro-2-methyl-4- oxa-fi-hydroxy-6-hydroxyethyl hexane which is reduced as in Example I to provide 2-methyl-4-oxa6-hydroxy-6- hydroxyethyl-Z-hexylamine.

Genetically, the novel compounds of the present invention can be represented by the formula R1 R1(IIJ(CHR4) x- 2 wherein R is a member selected from the group consisting of methyl and hydrogen; wherein R is a member selected from the group consisting of alkyl radicals of about 1 to 20 carbon atoms; lower hydroXyalkyl radicals; and a radical having the general formula:

' (CH2)X R2 R is a member selected firom the group consisting of the radicals:

[OCHz-(|3H] OH wherein R is a member selected from the group consist ing of hydrogen, phenyl, Intro-substituted phenyl, halosubstituted phenyl, alkyl, hydroXy-substituted alkyl, halosubstituted alkyl, alkene, and phenyl-substituted alkyl radicals; y is an integer ranging from 1 to 20; x is an integer ranging from 1 to 20; and Z is selected from the group consisting of N and NH It is claimed:

matter having the general for- 1. A composition of mula:

R1 i H2)x[O-CH2C|H],'OH v wherein R is analkyl radical of about 1 to 20 carbon atoms; R is a member selected from the group consisting of hydrogen, alkyl and hydroxy-substituted alkyl; y is an integer ranging from 1 to 20; and x is an integer ranging from 1 to 20.

2. The compound 2-rnethyl-2-nitro-4 oxa-6-hydroxyhexane.

References Cited by the Examiner UNITED STATES PATENTS 2,067,385 1/1937 Evans et a1.

2,282,646 5/1942 De Groote et al 260-584 2,483,739 10/1949 Roach et al. 26O6l5 2,491,533 12/1949 Swern 260-615 2,668,805 2/ 1954 Greenlee.

2,798,873 7/1957 Matter et al 260-484 X 2,871,266 1/1959 Riley 260584 3,021,341 2/1962 Croxall et a1 2606l5 X JOSEPH R. LIBERMAN, Primary Examiner.

CHARLES B. PARKER, LORRAINE A. WEIN- BERGER, Examiners.

R. V. HINES, H. T. MARS, Assistant Examiners. 

1. A COMPOSITION OF MATTER HAVING THE GENERAL FORMULA: 